5-(t-butyl-1,3,4-thiadiazol-2-yl)-3-methyl-5-hydroxyimidazolidin-2-ore

ABSTRACT

This invention discloses the compound 1-(5-t-butyl-1,3,4thiadiazol-2-yl)-3-methyl-5-hydroxy-1,3-imidazolidin-2-one and its use as a herbicide.

United States Patent [191 Krenzer [451 Sept. 9, 1975 [5 S-(T-BUTYL-l,3,4-THlADIAZOL-2-YL)-3- METHYL-S-HYDROXYIIVHDAZOLIDIN-Z- ORE [75] Inventor: John Krenzer, Oak Park, Ill.

[73] Assignee: Velsicol Chemical Corporation,

Chicago, Ill.

[22] Filed: Feb. 11, 1974 [2]] Appl. No.: 441,721

Related U.S. Application Data [63] C0ntinuation-in-part of Ser. No. 383,417, July 27,

1973, abandoned.

[52] U.S. Cl. 260/3063 D; 71/90 [51] Int. CL C07D 417/04 Primary Examiner'Richard J. Gallagher Attorney, Agent, or Firm-Robert J. Schwarz; Dietmar H. Olesch ABSTRACT This invention discloses the compound I-(S-t-butyl- 1 ,3,4-thiadiazol-2-yl)-3-methyl-5-hydroxyl ,3- imidazolidin-Z-one and its use as a herbicide.

1 Claim, No Drawings 1 -(T-BUTYL-1,3,4-THlADIAZOL-2-YL)-3- METHYL-5-HYDROXYIMlDAZOLlDIN-2-0RE This application is a continuation in part of copending application Ser. No. 383,417, filed July 27, 1973, now abandoned.

This invention relates to a new composition of matter and more specifically relates to the compound l-(5-tbutyl- 1 ,3,4-thiadiazol-2-yl )-3-methyl-5-hydroxyl ,3- imidazolidin-2-one. The compound of the present invention has the following structural formula:

The compound of the present invention has unexpected utility as a herbicide.

The manner in which the compound of this invention can be prepared readily is illustrated in the following examples.

EXAMPLE 1 Preparation of S-t-Butyl- 1 ,3,4-thiadiazol-2-yl lsocyanate Dimer A saturated solution of phosgene in ethyl acetate (100 ml) was charged into a glass reaction vessel equipped with a mechanical stirrer. A slurry of 5-tbutyl-2-amino-l ,3,4-thiadiazole grams) in ethyl acetate (300 ml) was added to the reaction vessel and the resulting mixture was stirred for a period of about 16 hours resulting in the formation of a precipitate. The

reaction mixture was then purged with nitrogen gas to remove unreacted phosgene. The purged mixture was then filtered to recover the desired product S-t-butyl- 1,3,4-thiadiazol-2-yl isocyanate dimer as a solid having a melting point of 261 to 263C.

EXAMPLE 2 Preparation of the Dimethyl Acetal of 2-[ l-methyl-3-(5-t-butyl-1,3,4-thiadiazol'2- yl )ureido acetaldehyde EXAMPLE 3 Preparation of i 1-( S-t-Butyll ,3 ,4-thiadiazol-2-yl )-3-methyl-5- hydroxy- 1 ,3-imidazolidin-2-one The dimethyl acetal of 2-[l-methyl-3-(5-t-butyl- 1,3,4-thiadiazol-2-yl)ureido]acetaldehyde 16 grams),

concentrated hydrochloric acid (10 ml) and water (500 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture was heated at reflux for a period of about 15 minutes. The reaction mixture was filtered While hot and the filtrate was then cooled, resulting in the formation of a precipitate. The precipitate was recovered by filtration, dried and was recrystallized from a benzene-hexane mixture to yield the desired product I-(S-t-butyl-l ,3,4-thiadiazol-2-yl)- 3-methyl-5-hydroxy-1,3-imidazolidin-2-one having a melting point of 133 to 134C.

For practical use as a herbicide the compound of this invention" is generally incorporated into herbicidal compositions which comprise an inert carrier and a herbicidally toxic amount of the compound. Such herbicidal compositions, which can also be called formulations, enable the active compound to be applied conveniently to the site of the weed infestation in any desired quantity. These compositions can be solids such as dusts, granules, or wettable powders; or they can be liquids such as solutions, aerosols, or emulsifiable concentrates.

For example, dusts can be prepared by grinding and blending the active compound with a solid inert carrier such as the talcs, clays, silicas, pyrophyllite, and the like. Granular formulations can. be prepared by impregnating. the compound, usually dissolved in a suitable solvent, onto and into granulated carriers such as the attapulgites or the vermiculites, usually of a particle size range of from about 0.3 to 1.5 mm. Wettable powders, which can be dispersed in water or oil to any desired concentration of the active compound, can be prepared by incorporating wetting agents into concentrated dust compositions.

In some cases the active compound is sufficiently soluble in common organic solvents such as kerosene or xylene so that it can be used directly as a solution in these solvents. Frequently, solutions of herbicides can be dispersed under superatmospheric pressure as aerosols. However, preferred liquid herbicidal compositions are emulsifiable concentrates, which comprise the active compound according to this invention and as the inert carrier, a solvent and an emulsifier. Such emulsifiable concentrates can be extended with water and/or oil to any desired concentration of active compound for application as sprays to the site of the weed infestation. The emulsifiers most commonly used in these concentrates are nonionic or mixtures of nonionic with anionic surface-active agents. With the use of some emulsifier systems an inverted emulsion (water in oil) can be prepared for direct application to weed infestations.

A typical herbicidal composition according to this invention is illustrated by the following example, in which the quantities are in parts by weight.

Example 4 Preparation of a Dust Product of Example 3 10 Powdered Talc The above ingredients are mixed in a mechanical grinder-blender and are ground until a homogeneous, free-flowing dust of the desired particle size is obtained. This dust is suitable for direct application to the site of the weed infestation.

The compound of this invention can be applied as a herbicide in any manner recognized by the art. One method for the control of weeds comprises contacting the locus of said weeds with a herbicidal composition comprising an inert carrier and as an essential active ingredient, in a quantity which is herbicidally toxic to said weeds, the compound of the present invention. The concentration of the new compound of this invention in the herbicidal compositions will vary greatly with the type of formulation and the purpose for which it is designed, but generally the herbicidal compositions will comprise from about 0.05 to about 95 percent by weight of the active compound of this invention. In a preferred embodiment of this invention, the herbicidal compositions will comprise from about 5 to about 75 percent by weight of the active compound. The compositions can also comprise such additional substances as other pesticides, such as insecticides, nematocides, fungicides, and the like; stabilizers, spreaders, deactivators, adhesives, stickers, fertilizers, activators, synergists, and the like.

The compound of the present invention is also useful when combined with other herbicides and/or defoliants dessicants, growth inhibitors, and the like in the herbicidal compositions heretofore described. These other materials can comprise from about 5 percent to about 95 percent of the active ingredients in the herbicidal compositions. Use of combinations of these other herbicides and/or defoliants, dessicants, etc. with the compound of the present invention provide herbicidal compositions which are more effective in controlling weeds and often provide results unattainable with separate compositions of the individual herbicides. The other herbicides, defoliants, dessicants and plant growth inhibitors, with which the compound of this invention can be used in the herbicidal compositions to control weeds, can include chlorophenoxy herbicides such as 2,4-D, 2,4,5-T, MCPA, MCPB, 4(2,4-DB, 2,4-DEB, 4-CPB, 4-CPA, 4-CPP, 2,4,5-TB, 2,4,5-TES, 3,4-DA, silvex and the like; carbamate herbicides such as IPC, CIPC, swep, barban, BCPC, CEPC, CPPC, and the like; thiocarbamate and dithiocarbamate herbicides suchas C DEC, metham sodium; EPT C, diallate, PEBC, perbulate, vernolate and the like; substituted urea herbicides such as norea, siduron, dichloral urea, chloroxuron, cycluron, fenuron, monuron, monuron TCA, diuron, linuron, monolinuron, neburon, buturon, trimeturon-and the like; symmetrical triazine herbicides such as simazine, chlorazine, atraone, desmetryne, norazine, ipazine, prometryn, atrazine, trietazine, simetone, prometone, propazine, ametryne, and the like; chloroacetamide herbicides such as alpha-chloro-N, N- dimethylacetamide, CDEA, CDAA, alpha-chloro-N- isopropylacetamide, 2-chloro-N-isopropylacetanilide, 4-( chloroacetyl) morpholine, l- (chloroacetyl)piperidine, and the like; chlorinated aliphatic acid herbicides such as TCA, dalapon, 2,3- dichloropropionic acid, 2,2,3-TPA and the like; chlorinated benzoic acid and phenylacetic acid herbicides such as 2,3,6-TBA, 2,3,5,6-TBA, dicamba, tricamba, amiben, fenac, PBA, 2-methoxy-3,6- dichlorophenylacetic acid, 3-methoxy-2,6- dichlorophenylacetic acid, 2-methoxy-3,5,6-trichlorophenylacetic acid, 2,4-dichloro-3-nitrobenzoic acid and the like; and such compounds as aminotriazole, maleic hydrazide, phenyl mercuric acetate, endothal,

biuret, technical chlordane, dimethyl 2,3,5,6-tetrachloroterephthalate, diquat, erbon, DNC, DNBP, dichlobenil, DPA, diphenamid, dipropalin, trifluralin, solan, dicryl, merphos, DMPA, DSMA, MSMA, potassium azide, acrolein, benefin, bensulide, AMS, broma- Ci], 2-( 3,4-dichlorophenyl)-4-methyl-l ,2,4- oxadiazolidine-3,5-dione, bromoxynil, cacodylic acid, CMA, CPMF, cypromid, DCB, DCPA, dichlone, diphenatril, DM'I'I', DNAP, EBEP, EXD, HCA, ioxynil, IPX, isocil, potassium cyanate, MAA, MAMA, MCPES, MCPP, MH, molinate, NPA, OCH, paraquat, PCP, picloram, DPA, PCA, pyrichlor, sesone, terbacil, terbutol, TCBA, brominil, CP-50l44, H-l76- l, H-732, M-290l planavin, sodium tetraborate, calcium cyanamid, DEF, ethyl xanthogen disulfide, sindone, sindone B, propanil and the like.

Such herbicides can also be used in the methods and compositions of this invention in the form of their salts, esters, amides, and other derivatives whenever applicable to the particular parent compounds.

Weeds are undesirable plants growing where they are not wanted, having no economic value, and interfering with the production of cultivated crops, with the growing of ornamental plants, or with the welfare of livestock. Many types of weeds are known, including annuals such as pigweed, lambsquarters, foxtail, crabgrass, wild mustard, field pennycress, ryegrass, goose-grass, chickweed, wild oats, velvetleaf, purslane, barnyard grass, smartweed, knotweed, cocklebur, Wild buckwheat, kochia, medic, corn cockle, ragweed, sowthistle, coffeeweed, croton, cuphea, dodder, fumitory, groundsel, hemp nettle, knawel, spurge, spurry, emex, jungle rice, pondweed, dog fennel, carpetweed, morning glory, bedstraw, ducksalad, naiad, cheatgrass, fall panicum, jimsonweed, witchgrass, switchgrass, watergrass, teaweed, wild turnip and sprangletop; biennials such as wild carrot, matricaria, wild barley, campion, chamomile, burdock, mullein, roundleaved mallow, bull thistle, hounds-tongue, moth mullein and purple star thistle; or perennials such as white cockle, perennial ryegrass, quackgrass, Johnson grass, Canada thistle, hedge bindweed, Bermuda grass, sheep sorrel, curly dock, nutgrass, field chickweed, dandelion, campanula, field bindweed, Russian knapweed, mesquite, toadflax, yarrow, aster, gromwell, horsetail, ironweed, sesbania, bulrush, cattail, winter-Cress, horsenettle, nutsedge, milkweed and sicklepod.

Similarly, such weeds can be classified as broadleaf or grassy weeds. It is economically desirable to control the growth of such weeds without damaging beneficial plants or livestock.

The new compound of this invention is particularly valuable for weed control because it is toxic to many species and groups of weeds while it is relatively nontoxic to many beneficial plants. The exact amount of the compound required will depend on a variety of factors, including the hardiness of the particular weed species, weather, type of soil, method of application, the kind of beneficial plants in the same area, and the like. Thus, while the application of up to only about one or two ounces of the active compound per acre may be sufficient for good control of a light infestation of weeds growing under adverse conditions, the application of ten pounds or more of active compound per acre may be required for good control of a dense infestation of hardy perennial weeds growing under favorable conditions.

The herbicidal toxicity of the new compound of this invention can be illustrated by many of the established testing techniques known to the art, such as preand post-emergence testing.

The herbicidal activity of the compound of this invention was demonstrated by experiments carried out for the pro-emergence control of a variety of weeds. In these experiments small plastic greenhouse pots filled with dry soil were seeded with the various weed seeds. Twenty-four hours or less after seeding the pots were sprayed with water until the soil was wet and the compound l-( S-t-butyll ,3,4-thiadiazol-2-yl )-3-methyl-5- hydroxy-l,3-imidazolidin-2-one formulated as a solution in an inert solvent was sprayed at the indicated concentrations on the surface of the soil.

After spraying, the soil containers were placed in the greenhouse and provided with supplementary heat as required and daily or more frequent watering. The plants were maintained under these conditions for a period of 27 days, at which time the condition of the plants and the degree of injury to the plants was rated on a scale offrom 0 to 10, as follows: 0 =no injury, 1,2 =slight injury, 3,4 =moderate injury, 5,6 =moderately severe injury, 7,8,9 =severe injury and =death. The effectiveness of the compound is demonstrated by the following data in Table I.

The herbicidal activity of the compound of this invention was also demonstrated by experiments carried out for the ipost-emergence control of a variety of weeds. In these experiments the compound of this invention was formulated as a solution in an inert solvent and sprayed at the indicated dosage on the foliage of the weeds that have attained a prescribed size. After spraying, the plants were placed in a greenhouse and watered daily or more frequently. Water was not applied to the foliage of the treated plants. The severity of the injury was determined 17 days after treatment and was rated on the scale of from 0 to 10 heretofore described. The effectiveness of the compound is demonstrated by the data in Table: ll.

TABLE II injury Rating Rate in lbs/acre Weed Species 5 2 Yellow nutscdgc Wild oats Jimsonwccd Pigwecd .lohnsongrass Vclvctleaf Mustard Yellow foxtail Barnyardgrass C rahgrass Cheatgrass Morningglory I0 I claim: l. The compound I-(S-t-butyl-l,3,4-thiadiazol-2-yl)- 3-methyl-5-hydroxy-l ,3-imidazolidin-2-one.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. B,9O +,6 +O Q Dated September 9, 1975 Inventor (s) John r It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

The term of this patent subsequent to August 26, 1992;

has been disclaimed.

. Signed and Scaled this [SEAL] A ttest:

RUTH. C. MASON C. MARSHALL DANN 8 ff Commissioner pj'Parenls and Trademark:

Thirteenth Day of July 1976 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECT-ION PATENT NO. I 3, 904,640

DATED September 9, 1975 INVENTOR( I John Krenzer It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

The title, both on the first page and in lines 1 and 2 of column 1,

appearing as "5- (T-BUTYL-l,3-,4THIADIAZOL-2YL) 3ME'I'HYL 5-HYDROXYIMIDAZOLIDIN"2-ORE should read 5" (EfBUTYL l, 3 4-THIADIAZOL-2-YL) -3-METHYL-S-HYDROXYIMIDAZQLIDIN- The formula in column 1, lines 13 through 19, appearing as N-N CH-----CH2 CH I 3 II II i l H C C-C C----N N -CH l CH S C ll 0 should be N--N CI-I--CH CH i 3 l I H C--CC C--N N----CH I CH S C ll 0 In column 3, line 38, for "4 (2,4-DB, read 4 (2,4-DBI) Signed and Scaled this twenty-third Day Of December 1975 [SEAL] A tres t:

RUTH C. MASON Arresting Officer C. MARSHALL DANN Commissioner ofPatenIs and Trademarks 

1. THE COMPOUND 1-(5-T-BUTYL-1,3,4-THIADIAZOL-2-YL)-3METHYL-5-HYDROXY-1,3-IMIDAZOLIDIN-2 -ONE. 